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UNIVERSITY  OF  ILLINOIS   BULLETIN 

I  ssr  HI)     WEEKLY 

Vol.  XI.  MAY   11.    I'M  (  No 

[Entered  as  second-class  matter  December    II,   I'M.',  at  the  post  offi 

L'rtiana,  Illinois,  under  the  A  ist  24.   1912.] 


BULLETIN  No.  19 

DEPARTMENT  OF  CERAMICS 

R.  T.  STULL,  Acting  Director 


INVESTIGATION  OX  IRON  ORK  CEMENTS 


BY 
ARTHUR  JE.  WILLIAMS 


PUBLISHED  BY  THE   UNIVERSITY  OF   ILLINOIS,  URBANA 


19  13     I  9  V4 


Authorised  Reprint  from  the  Copyrighted  i 
Volume  \  111.   1012 
NATIONAL  ASSOCIATION  OF  CEMENT  USERS. 

Pill!    MU    I    I   Ml  K.      I'lWI 

[RON   ORE  CEMENTS 

By  Aktih  h  E.  \\  ii.i.i wis.t 

Iron  ore  cement  is  a  producl  intended  to  be  used  in  sea  water 
work.  This  material  is  now  manufactured  in  Europe  under  tin- 
name  of  Erz  cement.  According  to  Mr.  William  Michaelis,  Jr.,J 
'•='-  the  process  of  manufacture  is  similar  to  that  of  Portland  cement 
except  that  limestone  and  iron  ore  axe  used  in  place  of  limestone 
and  clay.  United  States  Consul  Thackara§  gives  a  description 
of  its  manufacture  as  follows:  Chalk,  flintstone,  and  finely  ground 
ferric  oxide  are  used.  The  hint  and  iron  are  ground  together, 
then  mixed  with  the  chalk  and  water  and  BCreened  through  a 
fine  sieve.  The  screened  producl  is  clinkered  in  a  rotary  kiln 
and  then  ground.  An  average  composition  of  iron  ore  cement, 
given  by  Michaelis  is: 

CaO 63.5  per  cenl  Al:<>3 l  5  per  eenl 

Si02 20.5       "  Mn<> 1   5 

FejOj 11.0        "  Alkali 1.0 

The  effect  of  sea  water  is  undoubtedly  two-fold.  In  the  firsi 
place  chemical  reaction  may  take  place  between  certain  con- 
stituents of  the  cement  and  the  salts  in  sea  water,  and.  on  the 
other  hand,  the  mechanical  action  of  the  waves  carrying  large 
amounts  of  sand,  freezing,  thawing,  and  the  varying  pressure 

of  the  water  due  to  tide  help  to  injure  the  cement  BUbmerged  in 
sea  water.  This  work,  however,  will  be  confined  to  the  chemical 
action  of  sea  water,  for  the  mechanical  action  is  of  minor  import- 
ance unless  the  cement  is  weakened  by  chemical  changl 

The  reactions  which  take  place  between  Portland  cement 
and  sea  water  are  said  to  be  of  three  distinct  kinds.  First,  t  In- 
action of  MgCla  and  MgSt  )4  in  sea  water  on  the  calcium  hydrate 

formed  during  the  hardening  process  <>f  the  cement,  forming 
Mg(OH)a,  CaCl2,  and  CaS04.     Second,  the  action  of    gypsum, 

*  Under  tin-  direction  of  Mr   R   T  Stull. 

t  Orbana,  111.    A  Thesis   for   the  Bftcheloi  ol  - 

Illinois  in   1910. 

X  Eng.  Sms,  Vol   :■>..  pp.  545  646 

\  United  Statin  Consular  Reports,  June,  1008. 

(1) 


2  Williams  on  Iron  Ore  Cement. 

CaS04  formed  above,  upon  the  calcium  aluminates  forming 
calcium  sulpho  aluminate.  Third,  the  crystallization  of  the 
gypsum  and  calcium  sulpho  aluminate  giving  an  increase  in 
volume,  thus  causing  the  disintegration  of  the  mortar. 

That  free  lime  is  present  in  set  Portland  cements  is  well 
known.  Lamine*  found  32  per  cent  of  CaO  in  cement  sub- 
merged in  the  Black  Sea  15  years.  Every  analysis  of  a  cement 
exposed  to  sea  water  shows  a  high  percentage  of  MgO.  Yicatf 
in  1840  showed  this  fact  clearly,  a  cement,  which  was  submerged 
in  sea  water  for  6  months,  was  analyzed.  A  sample,  taken  from 
the  surface  exposed  to  the  sea,  showed  10.4  per  cent  MgO  and 
19.3  per  cent  CaO  while  the  interior,  which  was  not  impaired, 
showed  1.87  per  cent  MgO  and  31.33  per  cent  CaO. 

A.  MeyerJ  states  that  cement  loses  strength  in  sea  water. 
The  MgS04  acting  with  the  silicate  of  lime  forms  Mg(OH)2  and 
calcium  sulphate.  The  CaSO^  reacts  with  the  calcium  aluminates 
(A1203,  x  CaO)  of  the  cement,  forming  Al(OH)3  +  3  Mg(OH)2 
+  CaS04  +  CaCl2. 

Charles  J.  Potter§  says  that  MgS04  is  the  most  active  con- 
stituent in  sea  water  on  cement.  He  found  that  MgCl2  softens 
cement  but  causes  no  expansion.  Potter  says  that  it  is  now 
definitely  believed  that  magnesium  salts  act  on  the  feebly  com- 
bined lime  and  alumina  compounds  which  on  taking  up  water 
of  crystallization  cause  bursting  of  the  concrete.  He  mixed 
calcined  red  brick  clay  with  Portland  cement  clinker  in  propor- 
tions of  6  to  10.  From  this  mixture  briquettes  were  made  and 
placed,  together  with  Portland  cement  briquettes,  in  fresh  water, 
sea  water,  and  sea  water  to  which  10  per  cent  MgS04  was  added. 
Both  of  these  cements  gained  strength  in  fresh  water.  In  salt 
water,  the  Portland  cement  briquettes  began  to  fail  after  5  weeks 
and  were  disintegrated  after  5  years.  These  cements  showed 
blistering  after  one  year,  which  was  followed  by  expansion  and 
bursting.  The  red  cement  improved  continually  but  took  8 
weeks  to  obtain  the  maximum  strength  that  the  Portland  cement 
had  obtained  in  5  weeks.  In  the  10  per  cent  solution  of  MgS04, 
the  Portland  cement  tested  500  lb.  in  a  month  and  then  went 


*  Le  Ciment,  1901,  pp.  111-691-81. 

t  Iron  Ore  Cement — The  P.  C.  Co.  of  Hemmoor,  Hamburg,  Germany. 

t  Chemisches  Central  Blatt,  Vol.  73,  p.  1368. 

§  Jour.  Soc.  Chem.  Ind.,  Vol.  28. 


Williams  on    Ikon  Orb  CEMENT. 

back  to  zero  in  1  year.  The  red  cement  began  at  250  lb.  and 
increased  continually  to  1015  lb.  in  8  years.  Mr.  Potter  says 
thai  the  chemical  combination  <>f  CaO,  SiOj,  and  Al<»  and 
water  is  feeble  and  that  probably  accounts  for  the  ability  of 
magnesium  in  sea  water  to  be  bo  active. 

The  experiments  of  Dr.  Miehaelis*  and  l.e  Chatelierf  lead 
them  to  the  conclusion  thai  Portland  cemenl  Buffers  in  solutions 
containing  sulphuric  acid  salts,  which  applies  to  sea  water.  A 
douhle  salt  is  formed  composed  of  gypsum  and  calcium  aluminate. 
This  sulpho-alunhnate.  AUh.  CaO  +  3CaSC>4,  is  said  to  crystal- 
lize with  30  molecules  of  water,  which  process  musl  be  accom- 
panied by  considerable  expansion.  Le  ('hatcher  Bays  that  "the 
main  cause  it'  not  the  sole  cause,  of  the  injuries  which  cements 
suffer  under  the  action  of  sea  water  is  the  formation  of  calcium 
sulpho-alunhnate." 

RebuffatJ  says  on  the  contrary  that  sulpho-aluminates 
cannot  exisl  in  cements  in  sea  water  hut  agrees  with  Miehaelis 
and  Le  (hatcher  that  calcium  ahmiinates  are  the  part-  of  cement 
most  easily  acted  upon  by  salt-  in  sea  water. 

It  has  been  shown  that  calcium  ferrates  are  formed  similarly 
to  the  calcium  aluminates  and  that  alumina  could  he  replaced 
by  ferric  oxide  in  Portland  cement.  Dr.  Miehaelis  puts  this 
knowledge  into  use  with  the  idea  of  overcoming  the  disintegra- 
tion in  sea  water.  The  result  of  this  application  is  the  Iron  Ore 
cement  of  today. 

Dr.  Miehaelis  and  the  Royal  Experiment  Station  of  Charlot- 
tenburg  have  tested  these  cements  in  comparison  with  Portland 
cements  in  a  very  thorough  manner.  Mr.  William  Michaelis§ 
-ay-  in  a  paper  read  in  the  United  States  that  tests  of  Erz  cement 
and  Portland  cement  were  made  with  both  neat  and  '■'>  to  I  mix- 
tures which  were  placed  in  fresh   water,  sea   water,  and   water 

containing   five   time-    more   -alt    that    sea    water.       In    -ea    water. 

the  Krz  cement  developed  a  much  greater  strength  than  the 
Portland.  In  the  strong  -alt  water,  the  strength  of  the  Portland 
cemenl  decreased  rapidly  while  the  Irx  cemenl  showed  a  steady 
gain.     Briquettes  were  made  of  Iron  Ore  and  Portland  cement 

*  Ton  /•  to  I  ■•.  L896,  p.  838. 

i  I .  Ciment,  1901,  p  31   32 

:  T  •/.  1901,  i>   -'72. 

§  £Viy.  Newt,  Vol.  58,  pp  645  646 


4  Williams  on  Iron  Ore  Cement. 

which  were  placed  in  a  salt  solution  of  five  times  the  normal 
strength  of  sea  water  under  pressure  of  15  atmospheres  for  a 
few  days.  This  condition  destroyed  the  Portland  cement  bri- 
quettes entirely,  while  the  Iron  Ore  cement  increased  in  strength. 

The  Royal  Experiment  Station  conducted  similar  tests  to 
the  above  but  much  more  elaborate.  Two  Iron  Ore  and  three 
Portland  cements  were  made  into  prisms,  using  a  3  to  1  mixture 
of  standard  sand  and  cement.  These  prisms  were  placed  in 
sea  water  and  water  containing  five  times  the  percentage  of  salts 
in  ordinary  sea  water.  In  addition  to  this,  these  three  solutions 
were  allowed  to  act  upon  test  pieces  made  of  cement  mixed  with 
varied  amounts  of  gypsum.  All  the  Portland  cement  mortars 
disintegrated  in  the  three-  and  five-fold  salt  solutions;  all  the 
Iron  Ore  cement  mortars  remained  intact  and  sound. 

United  States  Consul  A.  W.  Thackara*  investigated  this 
cement  for  use  on  the  Panama  Canal.  The  result  of  his  investi- 
gations was  the  adoption  of  this  cement  for  concrete  work  exposed 
to  sea  water.  Another  point  in  favor  of  this  cement  is  the  property 
of  slower  setting.  The  cement  is  weaker  than  Portland  for  the 
first  week,  but  then  gradually  gains  strength  and  exceeds  that  of 
Portland. 

Publications  of  previous  experiments  do  not  show  definitely 
the  best  composition  for  cements  giving  the  greatest  protection 
against  sea  water.  With  this  idea  in  view,  the  following  investi- 
gations were  undertaken: 

The  outline  of  procedure  in  these  experiments  is  as  follows: 
Newberry's  cement  formula,  x  (3CaO,  Si02)  +  y(2CaO,  A1203), 
was  used  as  a  basis.  Assuming,  according  to  Xewberry,  that 
Fe203  could  replace  A1?03  and  form  2CaO,  Fe203,  a  triaxial  dia- 
gram was  plotted  (Fig.  1),  the  three  members  stationed  at  the 
three  corners  being  3CaO,  Si02,  2CaO,  A1203  and  2CaO,  Fe203. 
By  blending  these  three  members,  cements  could  be  obtained 
containing  various  amounts  of  the  calcium  aluminate  and  the 
calcium  ferrate. 

The  batch  weights  of  these  three  members  were  calculated 
and  about  15  kg.  of  each  were  weighed  up,  using  practically 
chemically  pure  materials.  Whiting,  flint,  aluminium  hydrate, 
and  red  oxide  of  iron  were  the  only  ingredients.     These  batches 

*  United  States  Consular  and  Trade  Reports,  June,  190S. 


Williams  on  Leon  <  >re  <  Iemen  i  . 

were  ground  in  a  ball  mill,  then  passed  through  a  200-mesh  Bieve; 
thus  getting  thorough  mixing  and  a  finely  ground  batch.     The 

formula1  for  the  cements  made  are  given  in  Table  I. 

The  following  cements,  No.   19,  20,  21,  22,  23,  24,  25,  36, 

37,  38,  39,  40,  42.  is.  49,  50,  51,  52,  53,  54,  58,  59,  60,  61  62, 
and  05  on  triaxial  diagram  were  then  weighed  up,  blunged  thor- 
oughly, and  partially  dried  by  pouring  the  slip  into  plaster  molds. 


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FIG.   1. — TRIAXIAL   DIM. HAM. 


The  cements  were  then  rolled  into  small  balls  aboul  the  size  of  a 
marble,  dried,  dehydrated  in  a  down  draft   kiln  to  about   Sl"> 
C.  and  placed  in  fruit  jars  ready  for  burning. 

These  cements  were  burnl  in  a  magnesite  tesl  kiln,  designed 
by  Mr.  Stull  of  the  Ceramic  Department,  especially  for  burning 
experimental  cements.  The  construction  of  this  kiln  ifl  Bhown 
in  Fig.  2.      The  success  of  this  kiln  is  a  noteworthy  fact   ae 


6 


Williams  on  Iron  Ore  Cement. 


kilns  suitable  for  this  purpose,  heretofore,  have  not  been  very 
satisfactory  owing  to  lack  of  control,  unevenness  of  temperature 
in  the  clinkering  chamber.  Kerosene  oil  was  used  for  fuel  with 
an  air  pressure  of  about  50  lb. 

The  temperature  at  the  time  the  clinker  was  drawn  from 
the  kiln  was  determined  first  by  means  of  a  "Wanner  pyrometer. 
This  was  given  up,  however,  as  the  rapid  rate  of  burning  required 
a  higher  temperature  than  the  true  temperature  of  clinker  forma- 
tion. 

Table  I. — Formulae  of  Cements  Made. 


No. 

Formula. 

Molecular  Ratio 
SiOiiAlO+FeiOa 

19 
20 
21 
22 

.l(3CaO,Si02)  +.2(2Ca0,Al203)  +.7(2Ca0,Fe203) 

0.11 

.l(3Ca0,Si02)  +  1  (2CaO,  AI1O3)  +  .8(2CaO,Fe203) 

0.11 

l(3CaO  SiOj)  +  O12CaO.Ff.O3) 

0.11 

.2(3CaO.Si02)  +.8(2CaO,Fe203) 

0.25 

23 

.2(3CaO,Si02)+.l(2Ca().AM)3)+.7(2CaO.Fc203) 

0.25 

24 

.2(3CaO.SiO-)+.2<2CaOAb03>  4-.6(2CaO,FeiOa) 

0.25 

25 

.2(3CaO.Si02)  +.3(2Ca<  '.Alt  >„>  -  5  2Ca<  >.F«-  ■■<  >.-,> 

0.25 

36 

3(3CaO.SiOi) +.2(2CaO  '■               >(2CaO.Fet< 

0.43 

37 

.3(3CaO.Si02)  4-.l(2Ca<  ».AK)a)  +  .6(2Ca0.Fe203) 

0.43 

38 

.3(3CaO.SiO-)  +.7(2CaO,Fe»03) 

0.43 

39 

.4(3Ca0.Si02)  +.6(2CaO,FejOa) 

(i  hi', 

40 

.4(3Ca0,Si02)+.l(2Ca<  i.AljO     -   5  2Ca<  »,Fe»Oa) 

0.66 

42 

.4(3CaO,SiOt)  +.3(2Ca<  >.A1  ■<  1  I  +.3(2Ca<  I.FesOa).. . 

0.66 

48 

.5(3Ca<  l,SiO      h.3(2CaO,AhO    +.2(2CaO,l  -  I  I 

1.00 

49 

.5(3CaO.Si02t  +2  2<  aO  \ .  ".   +.3(2CaO.Fe»Oa) 

1.00 

50 

.5(3CaO,SiOa)+.l(2CaO,AljO     -    1    !CaO,FejOa) . . . 

1.00 

51 

.5(3CaO,SiOj)  4-.5(2Ca<  >.¥<■<  la) 

1.00 

52 

.6(3CaO,SiO»)  4-.4(2Ca<  >.F.-  <  >  • 

1.50 

53 
54 
58 
59 
60 
61 
62 
65 

.6(3CaO,SiOi)  4-.l(2Ca<  i.Al-.Os)  4-.3(2CaO,FetO») 

1.50 

.6(3CaO,SiOt)  +.2(2CaO,Al20»)  +.2(2CaO.] 

1.50 

.7(5CaO.SiOj)+.2f2CaO.A!  Oa    +  1   2CaO.Fe*0  1 

2.33 

.7(3Ca0.Si02)  +.l(2Ca(  >.A1  ( )  1  +.2(2Ca<  >.Fe203) 

2.33 

.7(3Ca0,Si0s)  +.3(2CaO.F.   1  t})                       

2.33 

O.Si02) +.2(2CaO.Fej<  I  - 

4.00 

.8(3CaO.Si02)  -r  .1  2CaO,Al20  1  +  1   JCaO.FeaOa) 

4.00 

.9(3CaO,Si02)+.l(2CaO,Fe203) 

9.00 

Almost  all  of  these  cements  were  fused  till  the  surface  was 
glassy  in  appearance  before  the  cement  seemed  well  clinkered 
and  crystals  appeared.  Cements  No.  54,  58,  62,  and  65  appeared 
like  a  Portland  clinker,  except  darker  in  color  and  were  not  fused 
or  slag-like  in  appearance. 

The  clinker  was  first  reduced  in  a  jaw  crusher  and  then 
ground  in  a  disc  mill;  a  screen  test  showed  24.2  per  cent  on  150 
mesh  screen;  12.3  per  cent  on  200  mesh  screen;  and  the  remainder, 
63.5  per  cent  passed  200  mesh.  These  cements  show  that  the}' 
are  approximately  of  the  same  degree  of  fineness  as  the  average 
Portlands.     After  the  samples  were  ground,  pats  were  made  from 


Williams  on  [bon  Obi  Cement. 


'"     ^-J 

:- 

!     ! 

H- 

1 1  £*js 

"  ";tfl 

f:     ? 

i      i 

8 


Williams  on  Iron  Ore  Cement. 


them   in  the  usual  manner  to  determine  the  properties  of  the 

cement. 

The  amount  of  water  used  for  mortar  was  determined  by  the 
Boulonge  method  (Waterbury's  Cement  Manual,  p.  44).  The 
initial  and  final  sets  were  determined  with  Gilmore  needles. 

Four  pats  were  made  of  each  cement  with  the  idea  of  using 
one  for  the  time  of  setting  tests  and  placing  the  other  three  imme- 
diately in  the  moist  closet,  two  of  which  were  to  be  used  for  the 
boiling  test  after  24  hours,  the  third  to  be  allowed  to  stand  in 

Table  II. — Results  of  Tests  on  Cements. 


No. 


19 
20 
21 
22 
23 
24 
25 
36 
37 
38 
39 
40 
42 
48 
49 
50 
51 
52 
53 
54 
58 
59 
60 
61 
62 
65 


Time  of 

Initial    Set, 

hours. 


IX 

1 

2X 

1% 

1 

X 
1M 
1H 
l 
l 
2 
IX 

X 
IX 

ix 

3 
2 
1 

\X 
1 
1 

X 
IX 
l 

IX 
IX 


Time  of 

Final  Set, 

hours. 


Water 

Used, 

per  cent. 


3 

5 

5X 

4 

5H 

ii 

2X 

5 

8 

3X 

2% 

7 

3 

io 

9 

4 

4X 

3X 

4X 

5 

6 


21.0 
20.0 
21.0 
20.0 
21.0 
22.0 
21.5 
20.0 
20.0 
20.0 
21.0 
20.0 
21.5 
22.0 
21.0 
22.0 
21.0 
20.0 
21.0 
23.5 
22.0 
21.0 
21.0 
22.0 
22.0 
21.0 


Remarks 
at  Time  of 
Final  Set. 


Cracked  in  M  hour 

(  >.  K.  Strong 

No  cracks 

Small  cracks 

Cracked 

Cracked 

Cracked 

Cracked 

Cracked 

O.  K. 

Cracked 

Cracked 

O.  K. 

O.  K. 

Cracked 

Cracked 

O.K. 

Soft 

Cracked 

Cracked 

No  crack? 

(  >.  K. 

Soft  and  crumbly 

Warped 

Did  not  harden 

Cracked 


Conditions 
after  48  Hours 
in  Moist  Closet. 


Cracked 

Warped  and  cracked 

N<>  cracks 

No  cracks 

No  i  racks 

No  cracks 

No  cracks. 

O.  K. 

No  cracks 

No  cracks 

Cracked 

Warped 

No  cracks 

No  cracks 

Cracked 

No  cracks. 

Soft 

Soft 

No  cracks. 

No  cracks. 

Cracked 

Warped 

Warped  and  cracked 

O.  K. 

().  K. 

Warped 


Soft 


Soft 


o.  K 
O.  K. 


water  for  28  days.  All  of  these  cements  went  to  pieces  in  cold 
water  or  in  the  boiling  test.  The  results  are  given  in  Table  II. 
From  these  cements,  one  only,  i.  e.,  No.  62,  remained  sound 
when  placed  in  water.  This  cement  also  stood  the  boiling  test 
{\  hr.),  the  others  going  to  pieces.  The  molecular  ratio  of  Si02 
to  AI2O3  for  this  cement  is  four  and  since  the  molecular  ratio  for 
good  cements  is  between  5.1  and  6.8  and  since  none  of  these 
cements  lie  between  these  limits,  it  was  decided  to  construct  a 
new  group.  Cement  No.  62  approached  these  ratios  nearer  than 
any  other. 


Williams  on  [ron  «  )ke  Cement.  9 

A  new  batch  \\;is  calculated  after  Bleininger'a  formula 
(2.8CaO,Si02)  H  (2CaO,  AJA)  having  different  amounts  ol 
FegOa  and  Al,o,  and  also  the  ratio  of  SiOj  to  AU>,  |  I 
varied  from  jusl  above  to  jusl  below  the  limit-.  The  using  ol 
chemically  pure  raw  materials  in  place  of  Blag  and  limestone 
gives  less  efficient  mixtures  of  lime  andSiOj.  It  was,  therefore, 
thought  that  sufficient  lime  would  be  obtained  by  the  use  <>t 
Bleininger'a  formula.     For  formulae  Bee  Table  III. 

Table  III. — Formulae  fob  Cements  Mad 


No. 


.1, 

.1 
\ 
Bi 

1'.. 

n 

I.. 

C, 
Ci 


Formulae 


:,  i  .'  BCaO.Sil  I         »         FeO  I 

5  8  -'  B< ':.'  ».Si<  »«)  •    -'<  !a(  »,Fi  0 

6  l(2.8Ca<  '.Si<  It)  4-(2Ca<  l.FesO 

7  n  2  8Ca<  ».Si<  I.'  -  C2Ca<  1,1  ■  0 

5.25(2.8CaO,SiO       0  L75  21     O.AW3  B25(2I     O.FejO 

6.00(2.8CaO,SiO     •    l75(2CaO,AltOi)  •  B25(2Ca0.F<  0 

6  in  2  8Ca<  >,Si< >     -   200  2<  !a<  >.  \H  '  BOO  -'<  la<  >,FeiO 

7  22  .'  BCa<  >.Si(  h)  -hl75(2Ca<  »,A1»0     •  825(2Ca<  ».FejO 
.-,  ii  2.8<  la<  I.SiO              1(21     '  I   \i  iO  I  ■  640  -'<  !a<  ».F(  0 

5  v.,  2  BCaO.SiOil  I    WO  2CaO,  \1J 2B  O.F<  0 

6  in  2  8Ca<  >.Si<  i     •    MM  2CaO,Al»Oi)  •  2<     O.FejO 

7.00  -'  SCaO.SiOi    •    100  2Ca<  '.  \   I  I  800  -'<     '  l.FetO 


I'l.li.  is  I  USE   COMPOSn  Mis 


Molecular 

Xo. 

(  ..,  , 

AltOi 

FejOi 

Ratio 
RjO   3iO 

A, 

68.0 

0.0 

Hi. 

22   i 

:.   i 

At 

66.7 

0.0 

in    1 

22  9 

5  B 

Az 

67.2 

II  II 

9  ii 

6   i 

At 

67  5 

0   tl 

s  9 

23  6 

7    ii 

H, 

66   7 

1.3 

g  i 

Bt 

67    I 

11 

v     1 

•-':<  l 

6.00 

Bt 

67  5 

l  .3 

7   -v 

23    i 

6   in 

Hi 

68   l 

ii  M 

-  2 

Ci 

67    i 

2  ■". 

7  2 

....  i, 

6   ii 

C: 

68  0 

2  7 

6  ii 

Ci 

68  2 

2  .'. 

:,  8 

..   in 

- 

68   "• 

2 .  3 

:.   1 

7      MM 

These    Cements    were    prepared    ill    the    same    manner    except 

that  the  temperature  of  clinkering  was  determined  as  uear  as 

possible   by   the  method   used.       The   kiln   was  allowed   to  cool    to 

about  1000  deg.  C.  before  a  batch  of  cement  was  pu1  in  and  tem- 
perature was  then  gradually  raised  till  clinker  wa-  formed,  the 

temperature  was  then  read  with  a  Wanner  pyrometer. 

The  clinkers  obtained  appeared  exceptionally    good,   being 
dull  black  in  color  and  glistening  brightly  in  the  Bun.     These 


10 


Williams  on  Iron  Ore  Cement. 


clinkers  were  pulverized  the  same  as  has  been  previously  de- 
scribed, then  tested. 

The  results  of  these  tests,  Table  IV,  show  that  good  cements 
can  be  obtained  with  a  large  amount  of  alumina  using  the  same 
ratio  of  Si02  to  R203  as  Portland  cements  require.  One  very 
noticeable  fact,  however,  is  that  when  no  Al>03  is  present  as  in 
series  A,  A2,  As,  and  A±  these  cements  all  show  expansion,  thus 
giving  evidence  of  free  lime.  Although  A\  stood  the  boiling  test, 
the  cubes  made  from  this  cement  bulged  out  from  the  mold 
considerably. 

The  question  arises  at  this  point,  is  it  always  necessary  for 
A1203  to  be  present  or  can  a  good  cement  be  made  without  it? 


Table  IV. — Results  of  Test. 


Temperature 

Time  to 

Clinker, 

hours. 

when 

Appearance 

Initial    Set. 

Final  Set, 

H2O, 

No. 

Clinkered, 
deg.  C. 

of  C'iinker. 

hours. 

hours. 

per  cent. 

.-li 

1300 

:14 

24 

62 

24.8 

As 

1320 

Yi 

All 

22 

56 

24.0 

As 

1320 

m 

clinkered 

26 

56 

23.2 

.44 

1330 

lA 

good, 

28 

60 

26.0 

Bx 

1390 

Vl 

colored  black 

4M 

40 

26.3 

B2 

1320 

Wi 

and 

4H 

44 

24.4 

B3 

1350 

% 

glistening 

11 

36 

28.0 

Bt 

1400 

IH 

with 

5 

48 

IT,   O 

Ci 

1320 

14 

crystals 

5 

30 

24 . 4 

d 

1320 

;, 

in  a 

12 

40 

24.0 

d 

1330 

1  ;, 

bright 

12 

48 

28.0 

Ca 

1380 

M 

light 

17 

40 

27.2 

This  ought  to  be  possible  by  reducing  the  lime  content,  as  Ax 
was  the  best  of  series  A  and  also  had  the  smallest  amount  of 
lime  silicate. 

The  slowness  of  setting  is  another  factor  which  must  be 
considered.  It  will  be  seen  by  Table  IV  that  all  of  the  cements 
required  a  long  time  to  harden.  This  must  be  carried  on  in  a 
moist  atmosphere  also  or  the  cement  will  dry  out  before  it  has 
completely  hydrated  and  set.  The  above  factors  will  perhaps 
limit  the  use  of  this  cement  to  work  under  water  which  may  be 
allowed  to  set  a  considerable  time. 

All  the  cements  of  series  B  stood  a  6-hr.  boiling  test  with- 
out showing  any  signs  of  expansion.  In  series  C  all  but  C\  stood 
the  boiling  test,     d  warped  a  little  and  came  loose  from  the  glass 


Williams  on   Ikon  <  >ke  <  i  \n  \  i. 


11 


plate  although  the  cemenl  has  a  comparatively  l«»w  lime  content 
and  its  formula  lies  between  other  good  cements. 

The  attempt  was  next  made  to  give  these  cements  a  com- 
parative test  with  Portland  cement  i"  -how  their  relative  resist- 
ance to  sea  water.  The  method  used  was  Bimilar  to  that  <>f  Dr. 
Michaelis. 

One-inch  cubes  were  made  of  each  series  oi  cements  together 


&^ 


FIG.  3. — sTKAM   CYLINDER. 


with  a  8e1  of  cubes  of  a  standard  commercial  Portland  cement, 
which  had  stood  all  the  commercial  tests.  These  wen-  allowed 
to  stand  <»<)  hr.  in  the  moist  chamber  and  then  placed  in  water, 
remaining  in  water  for  27  days.  The  cubes  made  from  series  .1 
together  with  a  set  of  5  Portland  cement  cubes  were  placed  in  a 
steam  cylinder.  Fig.  :•;.  containing  an  artificial  Bea  water  Bolution 
of  ten  times  normal  strength.  The  quantity  of  salt  is  shown  in 
Table  V.      The    cement-    were    then    put     under    steam   pressure 


12 


Williams  ox  Irox  Ore  Cement. 


of  125  lb.  or  8|  atmospheres,  the  temperature  being  between 
150  and  200  cleg.  C.  This  was  continued  for  3  days.  On  opening 
the  cylinder,  the  salt  solution  was  found  to  be  very  dilute  due 
to  condensation  of  steam  and  no  visible  action  on  the  cements 
had  occurred.  The  salt  solution  and  cubes  were  then  put  into 
a  large  wide-mouthed  bottle,  provided  with  a  stopper  and  small 
vent  hole.  The  bottle  was  then  placed  inside  the  pressure 
cylinder  and  steam  admitted,  allowing  little  or  no  condensation. 
After  being  sure  that  the  bottle  was  not  broken  by  the  first  change 
in  temperature,  the  pressure  was  kept  on  for  3  days  longer. 
Upon  opening  the  cylinder,  the  cubes  were  found  bone  dry  and 
covered  with  salt  and  the  bottle  cracked.  This  was  due,  no 
doubt,  to  the  rapid  reduction  of  the  pressure,  allowing  the  water 


T 

\ble  V. — Analysis 

OF  Ska  Water.* 

Salt. 

Per  cent  of  Suit. 

Ten  times  per  cent 
of  Salt. 

Total  for  12  liters 
of  Water. 

XaCl 

MgCli 

MgSOj 

CaS04 

K-SO4 

77    7" 
10.87 
4 .  73 
3.60 
2.46 
0.217 
0.345 

108.7 
47.3 
36.0 

342.10 
478.28 
208.12 
158.  10 
10.80 

MgBr 

CaHC03 

0.93 
1.62 

37.3  parts  per  thousand  parts  water. 
100  parts  =2700  parts  water. 
12000 

=4.4  factor  times  per  cent  of  salt  =  quantity  per  12  liters  of  water. 

2700 


to  vaporize  rapidly,  which  was  at  a  temperature  above  its  boiling 
point. 

The  results  of  this  test  were  contrary  to  what  was  expected 
as  the  Portland  cements  were  untouched  and  all  of  the  iron 
cements  were  cracked  and  swollen.  This  cracking  and  swelling 
is  caused,  no  doubt,  by  an  excess  of  free  lime,  as  these  cements 
showed  an  expansion  in  the  boiling  test  and  there  was  a  deposit 
of  hydrated  lime  in  the  bottom  of  the  cylinder  which  seemed  to 
have  been  leached  out  of  the  cubes. 

Xo  crushing  strength  test  of  Series  A  was  made  as  they 
were  all  destroyed  already. 

Series  B  was  then  placed  in  the  cylinder,  with  a  set  of  Port- 


*  University  Geological  Survey  of  Kansis,  Vol.  7,  p.  27. 


Williams  on  Iron  I  mm:  I  !emen  i  . 


13 


land  cement  cubes.  A  vessel  made  of  l-in.  pipe  was  used  in 
place  of  the  glass  bottle  to  overcome  cracking  due  to  suddeu 
change  in  temperature.  This  series  was  kept  under  pressure  for 
6  days,  and  when  removed  from  the  cylinder  neither  the  Portland 
or  Iron  Ore  cements  appeared  harmed  excepl  cemenl  I!.,  which 
wtnt  to  pieces.  The  reason  for  the  disintegration  of  this  cemenl 
is  unexplainable  excepl  thai  il  was  do1  clinkered  properly.     The 

boiling  test,  however,  showed  a  good  cement.      (Table  VI.) 

As  the  crushing  strength  tests  of  the  Portlands  show,  there 
seemed  to  be  no  weakening  due  to  being  in  the  salt   solution. 


Table  VI. — Results  of  Boiling  Test  fob  »'»  Horns,  after  (>()  Hours  in 

Moist  Chamber. 


Number. 

Appearance  after 
s,;i  Water  Test. 

.4i 

Good, 
cracked  plate. 
Came  loose  from  plate  and  showed 
some  expansion. 

Same  asAj. 
Good. 

Came  loose  from  plate,  warped. 
Good. 
Good. 

Cracked. 

,i2 

At... 
At... 

•••( 

Bi 

Sound. 

Bt 

" 

Bi...                 

Wenl  '"  pii 

B, 

Sound. 

C\ 

Cracked  and  swollen. 

Ct 

Sound. 

Ca 

Ct...                 

Also  the  strength  of  the  Portlands  seems  to  average  higher  than 
the  Iron  Ore  cements.     (Table  VII.) 

Five  cubes  of  each  cement  of  Series  ('  were  then  placed  into 
the  cylinder  with  a  set  of  Portland  cubes  made  at  the  Bame  time. 
These  were  kept  under  pressure  for  8  days.  The  results  of  this 
series  were  quite  different  as  4  of  the  5  cemenl  cubes  were  badly 
cracked  and  had  begun  to  swell.  C2,  C»,  and  &  showed  no  signs 
of  disintegration,  but  (\  was  cracked  and  swollen  badly.  This 
cement,  as  the  A  Series,  did  not  stand  the  boiling  test  and  such 
an  action  would  be  expected  from  it  under  the  extreme  condi- 
tions in  the  pressure  cylinder.  The  crushing  strengths  of  Ct, 
C3,  and  d  averaged  lower  than  the  H  Series,  d  was  BO  BOfl  that 
disintegration  had  evidently  set   in. 


14 


Williams  on  Iron  Ore  Cement. 


Table  VII. — Crushing  Strength  of  Cements. 


No. 


P: 


Cross-sect  ional 
Area,  sq.  in. 


Crushing  Strength. 


Total  lb. 


Lb.  per  sq.  in. 


Average, 
lb.  per  sq.  in. 


1.08 

7680 

0.975 

4780 

1.06 

6650 

1.045 

5650 

1 .  105 

7750 

Pi  =  Portlands  in  fresh  water  3  weeks. 
7100 
4900 
6280 
4910 
7020 

p.2=Portland  cement  in  fresh  water  4  weeks. 
0.97  7850  8700 

0.95  6620  6970 

0 . 97  7730  7960 

P=pressure  with  Series  B  of  the  Iron  Ore  Cements. 


6042 


7876 


p 

0.97 

5420 

5590 

1.25 

IM.II 

3S90* 

1.025 

7650 

7470 

(i  as 

7330 

7470 

1.01 

7200 

7150 

6920 

Iron  Ore  Cement 

in  salt  solution  under  pressure  cylinder 

i  days. 

Bi 

1  .035 

5810 

5620 

1   n7.-, 

6720 

6250 

1.035 

:,  1  _'i  i 

4915 

1.06 

4740 

1460 

1  .045 

5200 

I  SCO 

5241 

B» 

1  .  105 

717H 

6500 

1.02 

6620 

6000 

1   1 155 

7500 

7  H  in 

1.115 

8430 

7550 

1.125 

6680 

5930 

6616 

B 

1   09 

1480 

11  2D 

1  .075 

5180 

1820 

I    in 

5000 

1540 

1   06 

6610 

6240 

1.12 

6000 

5350 

5014 

C2 

1.025 

4200 

4080 

1.03 

5400 

4360 

1  .  025 

6320 

6660 

1.1 

5N.-)() 

5310 

1.04 

4850 

4660 

4914 

C3 

1.05 

2280 

2190 

0.97 

1580 

1660 

1.1 

2640 

2400 

1.00 

ls.'H 

1880 

1.01 

2500 

2480 

2110 

C, 

1.07 

5220 

3000 

1.07 

6630 

6150* 

1    in, 

3630 

3330 

1.07 

5140 

4800 

1.04 

4050 

3900 

5757 

Port  Ian 

ds  in  Cylinder  7  day 

s  with  Series  C. 

P 

0.99 

3000 

3030 

P 

0.97 

6720 

6930* 
Only     unaffected 
Portland  cement 
cube. 

*  Signifies  not  calculated  in  average. 


Willi  IMS  ON    [RON   (  >ki:  I  1  \n  \  i .  |."> 

(  "om  i.i  BION8. 

As  tlu1  time  for  this  investigation  was  limited,  further  work 
could  not   be  done,  and  the  conclusions  which   may  I"'  drawn 

from  these  results  are  limited.     This  much  may  be  -aid.  however: 

1.  The  amount  of  lime  or  silicate  of  lime  ought  to  be  less 
when  l-Vjt);  alone  is  used  in  place  of  Ab<>;.  a-  the  lowesl  ratio 
of  Series  .1  5.1  was  the  only  one  which  stood  the  boiling  test. 
Series  H  showed  that  the  limits  gave  lined  cements  throughout, 
neglecting  Bj  which  must  have  disintegrated  due  to  some  other 
cause.  Series  c  showed  that  the  lime  and  silica  required  increased 
as  the  lower  ratio  f>.44  disintegrated  and  the  higher  ratios  were 
good.  To  sum  this  up,  when  all  iron  is  used  the  R_<  h  :  Si<  L 
ratio  should  he  below  5.1;  when  0.17.")  to  0.2  mols.  \U  >  i-  used 
with  0.825  to  0.8  mols.  of  Fe,(  ):i  the  ratios  li,.  between  5.1  to 
7.22.  If  O.'M)  to  0.4  mols.  of  Ab< )..;  the  ratio  must  he  5.8  or  greater. 
This  is  hut  a  suggestion  and  will  require  further  experimenting 
to  show  it  definitely. 

2.  That  cements  with  large  amounts  of  Fe^  h  will  stand  saline 
solutions  better  than  cements  containing  Ab<  b  was  shown  in 
the  test  of  Series  ('  where  the  Portlands  were  actually  disinte- 
grated and  the  iron  cements  stood  the  same  test. 

3.  The  results  seem  to  surest  that  if  the  amount  of  lime  was 
reduced  lower  than  2.8  CaO  in  Bleininger's  formula,  better  strength 
could  be  obtained.  There  was  found  in  the  bottom  of  the  vessel, 
after  each  trial  in  the  cylinder,  a  heavy  muddy  deposit  which 
was  principally  hydrated  lime  and  which  appeared  to  have  been 
leached  from  the  cubes.  This  reduction  of  the  amount  of  lime 
may  not  need  to  be  as  much  as  the  results  suggest  if  the  raw- 
materials  were  clay  and  limestone  in  place  of  pure  whiting, 
Al2(OH)6  and  flint.  All  of  the  iron  cements  would  have  stood 
the  tots  better  if  they  had  been  allowed  to  stand  in  the  atmosphere 
and  age,  thus  giving  the  lime  time  to  become  calcium  carbonate. 
The  Portland  cement,  which  these  cement-  were  tested  against, 

was  one  of  the  besl  cement-  on  the  market.  It  tested  as  follows: 
Initial  set.  3  hr.;  final  set  1  \  hi.;  tensile  Strength  of  neat  cement 
after  seven  days,  679  lb.;  after  28  days.  771  lb.:  and  it>  crushing 
strength  is  shown  in  the  table-.  This  cement  had  also  aged 
several  months  in  the  laboratory  and  was  in  the  best  of  condition 


16  Williams  on  Iron  Ore  Cement. 

to  stand  accelerated  tests.  The  percent  of  lime  given  by  Mr. 
William  Michaelis  is  63.5  per  cent  with  a  small  amount  of  magnesia, 
MgO,  1.5  per  cent.  The  cements  made  for  this  thesis  are  all 
above  66  per  cent,  this  is  only  another  evidence  that  these  con- 
clusions are  correct  and  the  following  formula  is  suggested  as  the 
center  of  a  series  of  cements  for  further  experimenting: 

4(2.8  CaO,Si02)  0.8  (2  CaO,  Fe203)  0.2  (2  CaO,  A1203). 

from  this  vary  both  the  amount  of  Si02  and  CaO. 

Bibliography. 

William  Michaelis,  Jr.,  Engineering  Xeirs,  Vol.  .58,  pp.  04.5-646. 

Charles  J.  Potter,  Journal  Society  Chemical  Industry,  Vol.  28. 

Newberry,  Journal  Society  Chemical  Industry,  Vol.  1G,  No.  11. 

A.  Meyer,  Ckemisches  Central  Blatt,  Vol.  73,  p.  1369. 

A.  Spencer  and  E.  C.  Eckel,  Patent  No.  912,266,  U.  S. 

Karl  Zulkowski,  Chemische  Industrie,  1901. 

A.  W.  Thackara,  U.  S.  Consular  Reports,  June,  1908. 

Iron  Ore  Cement,  The  P.  C.  Co.  of  Hemmoor,  Hamburg,  Germany. 

Lamine,  he  Ciment,  1901,  pp.  Ill,  691,  81. 

Dr.  Michaelis,  Tom  Industrie  Zeitung,  1896,  p.  838. 

Rebuffat,  Tone  Industrie  Zeitung,  1901,  p.  272. 

Le  Chatelier,  Le  Ciment,  1901,  pp.  31-32. 


